Calcium sulfo aluminate cement with polymer

ABSTRACT

A calcium sulfoaluminate-based concrete with a permeability of less than 1000 Coulombs. Rapid-setting low chloride-ion permeability calcium sulfoaluminate (CSA) cements and concretes include CSA and a suitable polymer such as a sol-gel derived, organic-inorganic, silica based hybrid coating solutions of polystyrene-butylacrylate polymers containing active silanol groups protected by hydroxyl groups containing polyalcohol, or other polymers. Such polymers may be added as powders or as liquid in the finish mill. Other rapid-setting low chloride-ion permeability (CSA) cements and concretes include CSA with selected particle size distributions, and do not require use of any polymer. These CSA cements and concretes have low chloride-ion permeability, high early strength, fast setting times, low-shrinkage, and high freeze-thaw resistance.

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a Division of U.S. patent application Ser. No.14/224,739 filed Mar. 25, 2014, and now pending, which is a Division ofU.S. patent application Ser. No. 13/103,029 filed May 6, 2011, now U.S.Pat. No. 8,715,409, which claims priority to U.S. ProvisionalApplication Ser. No. 61/332,657 filed May 7, 2010, all of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

Concrete and mortar structures can degrade and even fail due to aging,freeze/thaw cycles, deicing salts, shrinkage cracking, and otherenvironmental effects. Reducing corrosion in reinforced steel concreteis a major challenge. Corrosion of reinforcing steel in a concretestructure is caused by natural environmental effects, such as reactionswith chloride ions from salt water and deicing salts applied to thesurface of the concrete. Chloride ions migrate through the concrete andcorrode the embedded reinforcing steel. The ability of chlorides tomigrate through the concrete is referred to as the chloride ionpermeability of the concrete. In low permeability concrete, the rate atwhich chloride ions come into contact with the steel is low, whichincreases the stability of the embedded steel.

The permeability of unmodified, ordinary Portland cement (OPC) rangesfrom 3,500 to 12,000 coulombs as determined by ASTM C 1202. Permeabilityis generally reported at the age of 28 days. Table I below lists thechloride-ion permeability of various concretes. The abbreviation w/c isthe water to cement ratio.

TABLE I Chloride Charge Passing Permeability (Coulombs) Typical ConcreteType High >4000 High w/c ratio (>0.60) conventional OPC concreteModerate 2000 to 4000 Moderate w/c ratio (0.40-0.50) conventional OPCconcrete Low 1000 to 2000 Low w/c (<0.40) conventional OPC concrete VeryLow  100 to 1000 Latex-modified concrete, internally sealed concreteNegligible  <100 Polymer-impregnated concrete, polymer concrete

Beginning in the 1960s or earlier, polymer latex was added to Portlandcement to provide a low permeability concrete, as described in U.S. Pat.Nos. 4,086,201, 3,043,790, and 3,895,953, incorporated herein byreference. As used in concrete, latex is known for its plasticizing andadhesion properties and can improve tensile strength, compressivestrength, and flexural strength, while also reducing permeability byfilling in the large porosity of OPC matrices. Latex modified concretehas been used for bridge deck overlays, patching, and full depthpavement repairs, as it tends to be more durable in environmentsinvolving intensive free-thaw cycles and exposure to high saltconcentrations.

Notwithstanding these advantages, latex modified concrete remains inlimited use. The high cost of the latex polymer is a significantdrawback. It is generally provided in two to three component systems,which complicates storage and handling. Indeed, storage and handling isa major factor in the cost of latex modified concrete. Since latexmodified concrete has a short working time, it must be placed soon aftermixing with OPC, and it cannot be transported over long distances.Consequently, a special mobile vehicle is required to store and dispensethe two or three part latex blend into the concrete mixer at or verynear to the job site. Typical latex modified concrete is 4-7 times moreexpensive than OPC concrete and is therefore only used in harshenvironments. Hence, improved, easier to handle low permeabilitycements, mortars and concretes are needed.

While low permeability, traditional OPC concretes have been successfullymanufactured, they still exhibit the undesirable characteristics of OPC:long setting times, low durability and high shrinkage. Rapid settingcements, such as those based on calcium sulfoaluminate as described inU.S. Pat. No. 3,860,433, incorporated herein by reference, have shortsetting times which allow re-opening of a bridge within hours of itsclosure instead of days.

SUMMARY OF THE INVENTION

Two new rapid-setting, low permeability cements (RSLPC) mortars, groutsand concretes have been invented. A first new RSLPC may include a blendof calcium sulfoaluminate cement with an aqueous silicate/siloxaneredispersible liquid or powder polymer. A second new low permeabilitycement may be a polymer-free calcium sulfoaluminate cement with aparticle size distribution that has been optimized to yield the lowpermeability. These two types of cements may be mixed with water, sand,aggregate, and other materials to make low permeability mortars, groutsand concretes.

I. DEFINITIONS AND ABBREVIATIONS USED IN THIS APPLICATION

Cement: any substance provided (at least at one time in themanufacturing process) in a powdered or granular form, that when mixedwith a suitable amount of water, can form a paste that can be placed,poured, or molded to set as a solid mass.

ASTM: The American Society for Testing and Materials

Rapid Chloride Ion Penetration: concrete property obtained from ASTMC1202, indication of the concrete ability to resist chloride ionpenetration.

Freeze-Thaw Resistance: concrete property obtained using ASTM C666, thestandard test method for resistance of concrete to rapid freezing andthawing.

Strength: physical property obtained from ASTM C39 (Standard Test Methodfor Compressive Strength of Cylindrical Concrete Specimens), ASTM C1404(Standard Test Method for Bond Strength of Adhesive Systems Used withConcrete as Measured by Direct Tension, ASTM C882 (Standard Test Methodfor Bond Strength of Epoxy-Resin Systems Used With Concrete by SlantShear), ASTM C418 (Abrasion Resistance of Concrete by Sandblasting).

Early Strength: attribute obtained from ASTM C191 which is the standardtest method for Time of Setting of Hydraulic Cement by Vicat Needle.

Shrinkage: property tested using ASTM C157 (Standard Test Method forLength Change of Hardened Hydraulic-Cement, Mortar, and Concrete).

Polymer: a polystyrene-butylacrylate polymer containing active silanolgroups protected by hydroxyl groups containing polyalcohol.

Polymer Cement: a cements such as Portland cement, calcium aluminate, ora calcium sulfoaluminate cement, mortar or concrete made using Polymer(or an equivalent)

OPC: Ordinary Portland cement.

w/c: water to cement ratio

RSLPC: Rapid Setting Low Permeability Cement

CSA: Calcium Sulfoaluminate

II. DETAILED DESCRIPTION OF LOW PERMEABILITY FAST SETTING POLYMER CEMENT

A low permeability fast-setting cement may be made from a fast settingcalcium sulfoaluminate cement and a polystyrene-butylacrylate polymer.The polymer contains active silanol groups that are protected byhydroxyl groups containing polyalcohol (referred to below simply as“Polymer”). The Polymer is a newly invented polymer available asPermguard™ polymer from Chemat Technology, Inc., Northridge, Calif. ThisPolymer is a sol-gel derived, organic-inorganic, silica based hybridcoating solution for anti-corrosion applications. While the organic partor the polymer provides the corrosion resistance, the inorganic part orthe silanol group can form a strong bond with inorganic substrates suchas sand, rock, and cement containing materials. The apparent workingmechanism of the Polymer is as follows:

Polymer-Si—OH+OH—Si-matrix (e.g. cement)→polymer-Si—O—Si-matrix+H2O

This Polymer does not readily polymerize or agglomerate and because theactive silanol group is under the protection of another polymer. ThePolymer provides anticorrosion and hydrophobic characteristics to thecement paste. The weight dosage of the Polymer is 0.01%-4.0% by weightof the cement.

Another polymer that may be used is polyvinylalcohol encapsulatedsiloxane available as Elotex Copra 900 from Akzo Nobel SPG LLC,Bridgewater, N.J. This polymer is different from the new ChematTechnologies polymer. Like Permguard, the Elotex Copra 900 polymerprovides anticorrosion and hydrophobic characteristics to a cementpaste.

While the Polymer additives can be added to a wide range of hydrauliccements, including and not limited to Portland and calcium aluminatecements, the amount of Polymer needed with such cements is nearly anorder of magnitude larger an what is required with calciumsulfoaluminate cement. A typical dosage for Portland cement is about 4-8times the amount used for fast-setting calcium sulfoaluminate cement,presumably because the porosity of non-CSA cements is larger.

The polymer modified CSA cements can be made in three ways. A firstmethod is to mechanically mix a dried Polymer powder to the drycement/mortar/concrete. To use a liquid Polymer, the liquid Polymer ispreferentially diluted with water before adding any liquid/water to drymaterials. The third method is to add the liquid Polymer during thecement manufacturing process in the finish mill, when the clinker isbeing ground. The liquid Polymer added at a controlled rate to theun-ground hydraulic clinker and ground in the finish mill to form afinished polymer-modified cement product. The temperatures in the finishmill of 80-110° C. do not alter or destroy the polymer.

Many times rapid-setting cements can be produced that sets too fast forpractical use. In this case, an organic retarder may be used such ascitric acid. A granular, powder or liquid citric acid can be introducedinto the cement in two ways. The first method is to mechanically mixcitric acid. If liquid citric acid is used, it may be added to waterbefore adding it to the cement. If granular citric acid is used, it maybe mixed with the dry cement before adding water. The second method isto add the liquid citric acid into the finish mill during the cementmanufacturing process.

The cement provides easy to use single component cement offeringfreeze-thaw resistance, low rapid chloride ion penetration, fast settingwith high early strength, low shrinkage, and corrosion resistance whenaggregates and water are added. The Polymer additive and cement mix maybe provided in both bagged and bulk applications. Bagged products aretypically used for smaller jobs such as for patching, doweling,anchoring, grouting, airport and highway general repairs. Bulk productsare generally for larger jobs such as repairing roadway pavement, bridgedecks, industrial floors, and garage decks, vertical and overheadrepairs.

Examples of Low Permeability, Fast Setting Sulfoaluminate Cement/PolymerConcrete Example 1

A typical bulk mix: Cement: 10-25% of total mix; Polymer: 0.01%-4.0%;Fine Aggregate (Sand): 10-70%; and Coarse Aggregate (⅜″-1″ Rock):10-70%.

Example 2

A typical bag mix: Cement: 15-50% of total mix; Polymer: 0.5%-4.0%; FineAggregate (Sand): 10-85%; and Coarse Aggregate (⅜″-1″ Rock): 0-60%

The physical parameters are based on a bulk 7-sack bridge deck overlaymix design 17.75% Cement, 39.10% Coarse Aggregate, 43.15% Fine Aggregatewith water to cement ratio 0.45:

Concrete Characteristics

ASTM C191 Setting Time (Vicat): Initial Set: 15-40 minutes. Final Set:25-50 minutes.

ASTM C39 Compressive Strength

2 hours: 2000-4000 psi; 3 hours: 3000-5000 psi; 6 hours: 4000-6000 psi;24 hours: 6000-8000 psi; 7 days: 6000-9000 psi; 28 days: 6000-10000 psi.

TABLE 2 Physical Characteristics of Low Permeability Concrete ASTM C882Bond Strength ASTM C1202 Rapid Chloride Ion 24 hours: 1000-1500 psiPenetration 7 days: 1500-2500 psi 28 days: 10-900 coulombs 28 days:2000-3000 psi ASTM C157 Length Change ASTM C666 Freeze-Thaw 7 days:0.003% 300 cycles (Durability Factor): 98-105 28 days: 0.023% 1000cycles (Durability Factor): 115 ASTM C1404 Tensile Bond Specific Gravityof Cement Strength 2.85-3.00 g/cm³ 24 hours: 200-300 psi ASTM C418Abrasion Resistance Mass of Clay: 3.86 grams Cavity Volume: 1.93 (cm3),0.118 (in3)

The values in Table 2 above may vary with retarder dosages,environmental effects, aggregate properties, and other projectvariables. The physical parameters are based on a bagged mortar mixdesign 32.79% Cement, 0.55% Melamine Sulfonate superplasticizer, 66.66%Washed Concrete Sand (ASTM C33) with water to cement ratio 0.40.

TABLE 3 Physical Characteristics of Low Permeability Mortar ASTM C191Setting Time (Vicat): Initial Set: 15-25 minutes. Final Set: 25-40minutes. ASTM C39 Compressive Strength ASTM C882 Bond Strength 3 hours:5000-6000 psi 24 hours: 1000-2000 psi 24 hours: 6000-8000 psi 7 days:2000-2500 psi 7 days: 8000-9000 psi 28 days: 2300-3000 psi 28 days:8500-10000 psi ASTM C1202 Rapid Chloride Ion ASTM C157 Length ChangePenetration 7 days: 0.003% 28 days: 50-900 coulombs 28 days: 0.023% ASTMC666 Freeze-Thaw Specific Gravity of Cement 300 cycles (DurabilityFactor): 98-105; 2.85-3.00 g/cm³ weight loss %: 0.22%. 1000 cycles(Durability Factor): 115; weight loss %: 0.32%.

All tests were run in accordance with each individual ASTM method.Again, the values stated here may vary with retarder dosing,environmental effects of the localized area, aggregate properties, andother field conditions.

TABLE 4 Manufacture of Low Permeability, polymer-modified Rapid SettingCSA Cement through grinding into a finish mill. Clean Clinker LiquidPotable Gypsum Wt. Gypsum Polymer Water Mix No. Clinker % % (grams)(grams) (mL) (mL) 1 94 6 1410 90 9 0 2 94 6 1410 90 18 0 3 94 6 1410 9036 0 4 94 6 1410 90 36 36 5 94 6 1410 90 36 108

Water was added to the liquid Polymer to determine its optimum dosageinto the cement.

Procedure

1. The laboratory ball mill was heated to 100° C. The ball milltemperature was monitored using an infrared thermometer gun. 100° C. isa typical temperature for a cement finish mill.

2. 1410 g of clinker added to the mill.

3. 90 g of gypsum added to the mill.

4. The selected amount of Polymer was added into the mill at the onsetof grinding. This step was omitted for Mix 6 which is the control mix.

5. Grinding was stopped when a surface area of 6000 Blaine was achieved.

6. For mixes 4 and 5, the liquid Polymer and water was dissolved inwater prior to addition.

Results

TABLE 5 Physical Results of Low Permeability Cement with Liquid PolymerMortar Concrete Rapid Compressive Chloride Ion Low P Ball Strength ASTMPenetration Mill Data C109* (psi) ASTM Blaine Set Times 1.5 24 C1202 MixSurface Area Flow Initial Set Final Set Hours Hours 7 Days 28 Days 16140 72 (5) 15 min 21 min 4870 7590 10770 292 coulombs 2 6172 64 (5) 15min 21 min 4900 7690 10900 194 coulombs 3 7363 55 (5) 37 min  1 hr 110011200 12070 117 coulombs  2 min 4 5604 65 (5) 17 min 24 min 5010 813010820 406 coulombs 5 5816 59 (5) 15 min 20 min 3900 6600 10610 591coulombs

The C109 test protocol was altered with w/c=0.40 and cement/sand ratioat 50/50. The mix design for the concrete was the 7 sack bridge deckformulation mentioned previously.

As Table 5 indicates, all five rapid-setting CSA concretes exhibited apermeability of less than 1000 coulombs at 28 days of air curing, whichclassifies them as low permeability per ASTM C1202. Mixes with higheramounts of polymer had lower permeability Polymer was added in the labball mill as mentioned previous. This confirms that the polymer doesreduce chloride ion permeability. The permeability values were higherfor Mix 4 and Mix 5, in which the polymer content was reduced because ofdilution with water.

TABLE 6 Freeze-thaw resistance of polymer-modified, rapid setting CSAconcretes New York Hard Freeze Thaw (New York Test Method 502-3P)Results Mix Design Cycles Weight % Loss 1 0 1626 0.00% 2 0 1642 0.00% 30 1614 0.00% 4 0 1552 0.00% 5 0 1619 0.00% 1 25 1644 −1.09% 2 25 1657−0.91% 3 25 1624 −0.60% 4 25 1565 −0.90% 5 25 1635 −0.99% 1 33 1643−0.99% 2 33 1657 −0.91% 3 33 1624 −0.58% 4 33 1564 −0.83% 5 33 1639−1.25%

The freeze-thaw resistance of the concretes was tested using New YorkTest Method 502-3P. The normal test is typically run for 25 cycles. Herethe test was pushed to 33 cycles. The results are described in Table 6.Addition of the Polymer improved the freeze-thaw resistance of apolymer-free witness sample (Mix 1) when compared to Mix 5. Negativevalues shown in the table above illustrate weight gain in the sampleswith water. A positive value would illustrate weight loss which allsamples above did not occur. Increasing the polymer content (Mix 2 and3) in the cement shows the hydrophobic characteristic of the polymer. Anincrease in liquid polymer concentration (Mix 2 and 3) causes a lowerweight gain than witness sample (Mix 1). As the dosage of polymerincrease, the water intake of each sample decreases as shown throughMixes 1-3.

TABLE 7 Freeze-thaw resistance of rapid setting CSA concretes withCitric Acid # Average Cycles Weight % Loss % Loss Witness SampleUnmodified Cement Sample A 0.0 1519.1 0.00% 0.00% Sample B 1526.4 0.00%Sample A 2 1532.5 −0.88% −0.84% Sample B 1538.6 −0.80% Sample A 10.01521.7 −0.17% −0.61% Sample B 1542.3 −1.04% Sample A 14.0 1499 1.32%0.53% Sample B 1530.4 −0.26% Sample A 29.0 1462.7 3.71% 2.65% Sample B1502.1 1.59% Sample A 50.0 1452.5 4.38% 3.05% Sample B 1500.1 1.72%Modified Cement Sample with Citric Sample C 0 1501.7 0.00% 0.00% SampleD 1502.5 0.00% Sample C 2 1521.1 −1.29% −1.42% Sample D 1525.9 −1.56%Sample C 10 1552.5 −3.38% −3.70% Sample D 1563 −4.03% Sample C 14 1548.9−3.14% −3.56% Sample D 1562.3 −3.98% Sample C 29 1537.4 −2.38% −2.26%Sample D 1534.7 −2.14% Sample C 50 1528 −1.75% −2.06% Sample D 1538.1−2.37%

Additional freeze-thaw resistance in concrete can be provided by addingcitric acid. Results from Table 7 were tested using New York Test Method502-3P. The normal test is typically run out to 25 cycles. Here the testwas run further to 50 cycles. Addition of citric acid improved thefreeze-thaw resistance of the witness samples A and B when compared tosamples C and D. Negative values shown in the table above illustrateweight gain in the samples with water. A positive value would illustrateweight loss which samples A and B exhibited after the 14^(th) cycle.Samples C and D with citric acid had weight gain over the course of 50cycles.

Examples of Additives Suitable for the Manufacturing of LPRSC

A number of additives can be used in the manufacturing of lowpermeability rapid setting concrete. The list includes but is notlimited to, the following commercial or non-commercial additives

BASF Melflux 2651 F—Polycarboxylate based polymer (Carboyxlate-basedpolymerisate). This is a high range water reducer which is commerciallyavailable to concrete producers. This additive primarily is used toincrease the flow of the mortar/concrete material.

BASF Melment F10—Polymerized melamine sulfonate. This is a medium-rangewater reducer which is also commercially available to concreteproducers. This additive like the one above is used to increase the flowof the mortar/concrete material.

Citric Acid—Granular or liquid form. This additive is used to slow downhydration of a rapid-setting, otherwise non polymer-modified cement,concrete or mortar. This provides a longer working time which extendsthe initial and final set of the material. Citric acid may be added inthe finish mill at the cement production facility.

III. LOW PERMEABILITY POLYMER-FREE CALCIUM SULFOALUMINATE CEMENT

A low permeability calcium sulfoaluminate cement may also bemanufactured without any polymer or other additive, through careful andcontrolled optimization of the particle size distribution of the cement.Specifically, by minimizing the amount of larger particles having adiameter greater than 70 microns, or greater than 50 microns,permeability is significantly reduced. As one example, using a calciumsulfoaluminate cement wherein 98.36% pass through a 325 Mesh provides apermeability of 421 Coulombs. The chloride ion permeability of threecements of identical chemical composition but varying particle sizedistributions is presented below.

FIG. 1 shows the mass frequency percent of cement particles for calciumsulfoaluminate cement of a first sample. The majority of the particlesin the calcium sulfoaluminate cement in FIG. 1 are about 10 microns indiameter. FIG. 2 shows the percentage of particles of any given size,for the same cement as shown in FIG. 1. FIG. 3 shows the mass frequencypercent of cement particles for three additional samples of calciumsulfoaluminate cement. FIG. 4 shows the percentage of particles of anygiven size, for the same cements as shown in FIG. 3.

A cement comprises calcium sulfoaluminate cement particles; apolystyrene-butylacrylate polymer containing active silanol groups thatare protected by hydroxyl groups containing polyalcohol, with thepolymer comprising 0.01%-4.0% by weight of the cement. The cement mayhave one or more of the following characteristics: the polymer is asingle component additive; the cement is entirely free of latex; thepolymer comprising 0.5%-4.0% by weight; the polymer comprising a sol-gelderived, organic-inorganic, silica based hybrid coating solution; 97% ofthe cement particles are less than 40 microns; 85% of the cementparticles are less than 20 microns, optionally with 60% of cementparticles less than 10 microns, 35% less than 5 microns; 15% less than 2microns; and 8% less than 1 micron.

A cement suitable for a low permeability application may have thefollowing elemental analysis. The cement generally has a Blaine finenessof 5,500-7,500 with a 325 sieve fineness >98% passing. The table belowshows the analysis of the three different samples graphed in FIGS. 1 and2. Each sample (labeled RAPID-SET CEMENT) is a calcium sulfoaluminatecement

TABLE 8 Identification 000-087.SMP 000-088.SMP 000-089.SMP SAMPLERAPID-SET RAPID-SET RAPID-SET CEMENT CEMENT CEMENT Component % % % WetChemistry Analysis SiO2 15.14 15.08 13.62 Al2O3 15.12 15.43 15.77 Fe2O31.19 1.38 1.68 CaO 48.18 48.46 49.50 MgO 1.99 1.79 1.99 SO3 14.63 14.1713.96 K2O 0.46 0.47 0.00 Na2O 0.19 0.20 0.00 Total Alkalies 0.45 0.510.00 LOI 2.47 2.25 2.20 SUM 99.38 99.24 98.72 Physical Analysis Blaine6137 cm2/g 5900 cm2/g 5851 cm2/g Mesh (−325) 98.36% 97.71% 91.73%Chemistry Chlorides Water Solubles 370 ppm 390 ppm 300 ppm AcidChlorides 809 ppm 950 ppm 662 ppm (0.0809%) (0.0950%) (0.0662%) XRD CSA23.48% 23.43% 24.09% CS 10.23% 8.43% 9.39% Permeability ASTM C1202 28Days Air Cure 421 Coulombs 1580 Coulombs 3106 Coulombs

In the samples 087, 088 and 089 in Table 8 above, the Blaine surfaceareas are 6137, 5900 and 5851 cm²/g, and the permeabilities are 421,1580 and 3106 Coulombs, respectively. Relatively small changes in Blainenumber appear to result in relatively large changes in permeability.However, a Blaine measurement is a relatively rough and imprecisemeasurement that does not account for particle size distribution. Thepercentage of particles passing through a 325 mesh are 98.36%, 97.71%and 91.73%, respectively, for the above-mentioned permeabilities. Theseresults show that optimizing the particle size distribution by removingthe largest particles, without necessarily significantly altering thefine fraction of the cement, can reduce chloride ion permeability.

More specifically and referring to FIG. 1, the 088 and 089 samples havea much higher percentage of particles over 50 microns than sample 087.As shown in Table 8, these samples also have much higher permeabilitythan sample 087. These significant variations in permeability are notexplained by any variations in cement chemistry. The chemicalcompositions of all three cements, in term of oxide equivalents,crystalline compounds and total and soluble chlorides, were similar.

Many government agencies, such as the transportation departments ofvarious U.S. states, specify a permeability of less than 1000 Coulombsat the age of 28 days for bridge decks and other structures. Thispermeability can be achieved without the use of polymers or additive,through careful selection of particle fractions and particle sizedistribution, in the linker grinding process. FIG. 1 suggests that thismay be achieved, without any polymer or other additives, using a cementwhere particles greater than 70 microns comprise less than 0.05% by massof the cement, or where particles greater than 50 microns comprise lessthan 0.1% of the mass frequency. FIG. 2 suggests that a permeability ofless than 1000 Coulombs may be achieved with calcium sulfoaluminatecement where at least 60% of the particles have a diameter less than 10microns and at least 10% of the particles have a diameter less than 1micron.

Cement Milling and Grinding.

Cement is traditionally made by grinding cement clinker, gypsum, andother additives in a finish mill to obtain desired product fineness.Typically, a tube mill, commonly referred to as a ball mill is used forthis purpose. New technologies of finish mills include vertical rollermills (VRM) may also be used. Ball mills are cylindrical steel shellslined with high chrome alloys used to protect the outer shells. Themills are positioned horizontally, connected to a drive motor, whichturns the mill about its longitudinal axis.

Most modern ball mills are two chamber mills with a diaphragm separatingthe two compartments. The cements described can be successfully producedin single or two chamber mills. In a two-chamber mill, the first chamberis typically approximately 30% of the total length of the mill and isfilled with hardened steel or high chrome alloy balls ranging in sizefrom 50 mm to 90 mm.

Clinker and gypsum enter the mill through a feed chute from a mainclinker feed belt conveyor in a predetermined ratio to meet productspecifications—typically gypsum makes up 5-9% of the feed to the mill.The feed to this main conveyor belt is controlled by calibrated scalesand variable speed drives on the belts transporting clinker and gypsumfrom storage bins. In addition to the clinker and gypsum, variouschemical additives (liquid Polymer, citric acid, or any other additives)may be introduced in a liquid phase deposited directly on theclinker/gypsum mixture via pumps and discharge lines.

As the clinker and gypsum passes through the first chamber, it isreduced in size by the grinding action of the balls and also between theparticles themselves. The first chamber is used to break clinkernodules, which may exceed 200 mm. When the clinker is reduced toadequate size, typically around 2-3 mm, it passes through slots in thediaphragm and enters the second compartment for further grinding andsize reduction.

The finely ground powder is swept through the mill via fans into aseparator to segregate the larger particles of cement from those thatmeets predetermined density and fineness specification. The largerparticles are then reintroduced to the finish mill and re-circulatedthrough the process until the particle size distribution and fineness isachieved. The circulating load of material ranges from 200-300% using amechanical separator. Typical target specifications for low permeablecement are typically a Blaine of 6,200-7,000 cm2/g with >98% passing a325 mesh screen.

Thus, novel materials and methods have been described. Various changesand substitutions may of course be made without departing from thespirit and scope of the invention. The invention, therefore, should notbe limited except by the following claims, and their equivalents. In theclaims below, the content of any dependent claim may be combined withthe content any independent claim, as if the dependent claims weremultiply dependent.

The invention claimed is:
 1. A cement comprising: calcium sulfoaluminatecement particles; a polystyrene-butylacrylate polymer containing activesilanol groups that are protected by hydroxyl groups containingpolyalcohol, with the polymer comprising 0.01%-4.0% by weight of thecement.
 2. The cement of claim 1 wherein the polymer is a singlecomponent additive.
 3. The cement of claim 1 entirely free of latex. 4.The cement of claim 1 with the polymer comprising 0.5%-4.0% by weight.5. The cement of claim 1 with the polymer comprising a sol-gel derived,organic-inorganic, silica based hybrid coating solution.
 6. The cementof claim 1 wherein at least 97% of the cement particles are less than 40microns.
 7. The cement of claim 6 wherein at least 85% of the cementparticles are less than 20 microns.
 8. The cement of claim 7 wherein atleast 60% of the cement particles are less than 10 microns.
 9. Thecement of claim 8 wherein at least 35% of the cement particles are lessthan 5 microns.
 10. The cement of claim 9 wherein at least 15% of thecement particles are less than 2 microns.
 11. The cement of claim 10wherein at least 8% of the cement particles are less than 1 micron. 12.The cement of claim 1 wherein the polystyrene-butylacrylate polymercomprises a dry powder.
 13. The cement of claim 1 wherein thepolystyrene-butylacrylate polymer comprises a liquid.
 14. A cementcomprising: calcium sulfoaluminate cement; and apolystyrene-butylacrylate polymer containing active silanol groups thatare protected by hydroxyl groups containing polyalcohol, with thepolymer comprising 0.01%-4.0% by weight of the cement, and with thepolymer comprising a sol-gel derived, organic-inorganic, silica basedhybrid coating solution.
 15. The cement of claim 14 wherein at least 97%of the cement particles are less than 40 microns.
 16. The cement ofclaim 14 with the polymer comprising 0.5%-4.0% by weight.
 17. The cementof claim 16 wherein at least 60% of the cement particles are less than10 microns.
 18. The cement of claim 16 wherein at least 35% of thecement particles are less than 5 microns.
 19. The cement of claim 17wherein at least 15% of the cement particles are less than 2 microns.20. A cement comprising: calcium sulfoaluminate cement particles; apolystyrene-butylacrylate polymer containing active silanol groups thatare protected by hydroxyl groups containing polyalcohol, with thepolymer comprising 0.01%-4.0% by weight of the cement, wherein at least97% of the cement particles are less than 40 microns, at least 85% ofthe cement particles are less than 20 microns, at least 60% of thecement particles are less than 10 microns, and at least 35% of thecement particles are less than 5 microns.
 21. The cement of claim 20wherein at least 15% of the cement particles are less than 2 microns andat least 8% of the cement particles are less than 1 micron.